WO2005015608A2 - Method of inhibiting corrosion of copper plated or metallized surfaces and circuitry during semiconductor manufacturing processes - Google Patents
Method of inhibiting corrosion of copper plated or metallized surfaces and circuitry during semiconductor manufacturing processes Download PDFInfo
- Publication number
- WO2005015608A2 WO2005015608A2 PCT/US2004/017977 US2004017977W WO2005015608A2 WO 2005015608 A2 WO2005015608 A2 WO 2005015608A2 US 2004017977 W US2004017977 W US 2004017977W WO 2005015608 A2 WO2005015608 A2 WO 2005015608A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- corrosion inhibitor
- treatment bath
- fluid
- aqueous fluid
- concentration
- Prior art date
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 110
- 230000007797 corrosion Effects 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- 239000012530 fluid Substances 0.000 claims abstract description 98
- 239000003112 inhibitor Substances 0.000 claims abstract description 91
- -1 aromatic triazole Chemical class 0.000 claims abstract description 74
- 238000012544 monitoring process Methods 0.000 claims abstract description 34
- 239000012964 benzotriazole Substances 0.000 claims description 29
- 238000012546 transfer Methods 0.000 claims description 25
- 150000003852 triazoles Chemical class 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 7
- IPIVUPVIFPKFTG-UHFFFAOYSA-N 4-butyl-2h-benzotriazole Chemical compound CCCCC1=CC=CC2=C1N=NN2 IPIVUPVIFPKFTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 30
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 28
- 230000005284 excitation Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 150000003851 azoles Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000012921 fluorescence analysis Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- DNJANJSHTMOQOV-UHFFFAOYSA-N 4-bromo-2h-benzotriazole Chemical compound BrC1=CC=CC2=C1N=NN2 DNJANJSHTMOQOV-UHFFFAOYSA-N 0.000 description 1
- KMBINRQMOHJGIH-UHFFFAOYSA-N 4-bromo-5-(2-methylphenyl)-2h-triazole Chemical compound CC1=CC=CC=C1C1=NNN=C1Br KMBINRQMOHJGIH-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- JAQDPDHEBZHQGA-UHFFFAOYSA-N 4-chloro-5-(2-methylphenyl)-2h-triazole Chemical compound CC1=CC=CC=C1C1=NNN=C1Cl JAQDPDHEBZHQGA-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- BKZJXSDQOIUIIG-UHFFFAOYSA-N argon mercury Chemical compound [Ar].[Hg] BKZJXSDQOIUIIG-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006260 ethylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000004055 thiomethyl group Chemical group [H]SC([H])([H])* 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67057—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing with the semiconductor substrates being dipped in baths or vessels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67253—Process monitoring, e.g. flow or thickness monitoring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
- H01L22/20—Sequence of activities consisting of a plurality of measurements, corrections, marking or sorting steps
- H01L22/26—Acting in response to an ongoing measurement without interruption of processing, e.g. endpoint detection, in-situ thickness measurement
Definitions
- This invention relates to a method and apparatus for inhibiting corrosion of copper plated or metallized surfaces and circuitry in semiconductor devices immersed in water during semiconductor manufacturing processes using aromatic triazole corrosion inhibitors where the concentration of the corrosion inhibitor in the water is precisely monitored and controlled fluorometrically.
- BACKGROUND OF THE INVENTION Semiconductor chip manufacturers use a variety of azoles to prevent in-process manufacturing corrosion of copper plated or metallized surfaces and circuitry in the semiconductor devices.
- the chips are immersed in treatment baths containing a solution of ultra pure water and azole corrosion inhibitor.
- the azole content of the solution can be depleted, for example by chemical/physical adsorption onto the copper plated or metallized surfaces and circuitry, biodegradation, or by incidental dilution of the inhibiting solution with water that does not contain correct azole levels.
- azoles adsorb onto the surface of the semiconductor devices.
- azole is removed with the devices from the treating system resulting in a removal of corrosion inhibitor from the system with no significant fluid loss. Additional azole is removed from the system, along with fluid due to the adherence of the fluid to the semiconductor devices. Removal of azole through removal of copper-coated semiconductor devices is distinctive from traditional applications of azoles (such as open recirculating cooling water systems) where physical removal of treated surfaces from the system is not a routine occurrence. Corrosion protection while the chips are immersed in the treatment bath is essential to ensure that the semiconductor devices will work as intended. Corroded metal surfaces will not function properly in manufactured integrated circuits (reduced "yield") as compared to metal surfaces circuits that have been properly treated for corrosion inhibition.
- This invention is a method of inhibiting corrosion of copper plated or metallized surfaces and circuitry in semiconductor devices immersed in an aqueous fluid in a treatment bath comprising
- the present invention permits accurate and continuous control of aromatic triazole concentration within a specific concentration range in order to compensate for any processes leading to changes in triazole concentration during the manufacturing process or due to a desire by the operator to change triazole concentration at any point in the manufacturing process .
- FIG. 1 is a working curve for benzotriazole showing fluorescence intensity versus benzotriazole concentration in aqeuous solution at benzotriazole doses of 0, 1, 5, 10, 25, 50, 250, 500 and 1,000 ppm.
- FIG. 2 shows a typical treatment bath used in various manufacturing processes for copper plated or metallized semiconductor devices in which the semiconductor devices 5 are immersed in ultrapure water in a treatment bath 4 containing one or more fluid inlets 10 and fluid outlets 11.
- the treatment bath 4 includes means 16 such as a removable rack for supporting the semiconductor devices 5 in the treatment bath 4.
- Aromatic azole corrosion inhibitor solution contained in supply reservoir 1 is added into the treatment bath 4 using feeder line 2 through valve 3.
- Valve 3 may be replaced with or used in combination with a fluid addition pump (not shown).
- FIG. 3 shows an embodiment of this invention where the treatment bath 4 is equipped with means 12 for fluorometrically monitoring and controlling the concentration of aromatic azole corrosion inhibitors in the treatment bath where the monitoring and control means 12 are installed directly in a fluid transfer line 6.
- FIG. 4 shows an alternative embodiment of this invention where the monitoring and control means 12 are disposed along a side stream sample line 13 connected to a treatment bath fluid transfer line 6 through pump 14.
- This invention is a method of inhibiting corrosion of the copper plated or metallized surfaces and circuits in semiconductor devices while the devices are immersed in aqueous fluids in various stages of integrated circuit manufacturing processes.
- aqueous fluid means ultrapure water, or ultrapure water containing alcohols, organic solvents, or other processing additives typically used in the manufacture of semiconductor devices.
- semiconductor manufacturing process or “integrated circuit manufacturing process” includes all processes employed in the manufacture of these devices, including, for example, photolithography, etching, plating, doping, polishing, metallizing, and the like.
- aromatic triazole corrosion inhibitors are added to the aqueous fluid in an effective corrosion-inhibiting amount.
- Aromatic triazole corrosion inhibitors suitable for use in this invention include copper metal corrosion inhibitors comprising a triazole ring fused to an aromatic ring.
- Representative aromatic triazole corrosion inhibitors include benzotriazole, butylbenzotriazole, tolyltriazole, naphthotriazole, chlorobenzotriazole, bromobenzotriazole, chlorotolyltriazole, and bromotolyltriazole.
- “Tolyltriazole” includes 4-methylbenzotriazole and 5-methylbenzotriazole and mixtures thereof, including the mixtures disclosed in U.S. Patent No. 5,503,775, incorporated herein by reference.
- aromatic ring means substituted and unsubstituted aromatic carbocyclic radicals and substituted and unsubstituted heterocyclic radicals having about 5 to about 14 ring atoms.
- Representative aryl include phenyl, naphthyl, phenanthryl, anthracyl, pyridyl, furyl, pyrrolyl, quinolyl, thienyl, thiazolyl, pyrimidyl, indolyl, and the like.
- the aryl is optionally substituted with one or more groups selected from hydroxy, halogen, C ⁇ -C alkyl, C ⁇ -C 4 alkoxy, C ⁇ -C alkenyl, C ⁇ -C alkynyl, mercapto, sulfonyl, carboxyl, amino and amido.
- Preferred aromatic rings include phenyl and naphthyl.
- Alkoxy means an alkyl group attached to the parent molecular moiety through an oxygen atom. Representative alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and the like.
- Alkyl means a monovalent group derived from a straight or branched chain saturated hydrocarbon by the removal of a single hydrogen atom.
- alkyl groups include methyl, ethyl, n- and ⁇ o-propyl, n-, sec-, iso- and tert-butyl, and the like.
- Alkenyl means a monovalent group derived from a hydrocarbon containing at least one carbon-carbon double bond by the removal of a single hydrogen atom.
- Representative alkenyl groups include ethenyl, propenyl, butenyl, l-methyl-2-buten-l- yl, and the like.
- Alkynyl means a monovalent group derived from a hydrocarbon containing at least one carbon-carbon triple bond by the removal of a single hydrogen atom.
- Representative alkynyl groups include ethynyl, propynyl, 1- and 2-butynyl, and the like.
- “Amido” means a group of formula -C(O) NR'R" where R' and R" are as defined herein.
- Representative amido groups include methylaminocarbonyl, ethylaminocarbonyl, ⁇ o-propylaminocarbonyl and the like.
- “Amino” means a group having the structure -NR'R" wherein R' and R" are independently selected from H and C ⁇ -C 4 alkyl.
- Representative amino groups include amino (NH 2 ), dimethylamino, diethylamino, methylethylamino, and the like.
- Carboxyl means a group of formula -CO 2 H.
- Halogen means Br, Cl, F or I.
- Mercapto means a group of formula -SR' where R' is defined herein. Representative mercapto groups include -SH, thiomethyl (-SCH 3 ), thioethyl (- SCH 2 CH 3 ), and the like.
- Sulfonyl means a group of formula -SO H.
- Preferred aromatic triazole corrosion inhibitors are selected from the group consisting of benzotriazole, butylbeiizotriazole, tolyltriazole and naphthotriazole. Benzotriazole;, butylbenzotriazole, tolyltriazole are more preferred.
- the aromatic triazole corrosion inhibitor is typically added as a solution in alcohol or as aqueous solution with one or more alcohols.
- Suitable alcohols include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, triethanol amine, and the like.
- Representative corrosion inhibitor solutions comprise about 0.001 to about 50 weight percent aromatic triazole corrosion inhibitor.
- the aromatic triazole corrosion inhibitor is used in an amount sufficient to effectively prevent corrosion of the copper plated or metallized surfaces and circuitry of semiconductor devices without overdosing with inhibitor which then must be subsequently removed from the water.
- the dosage used is typically from about 1 ppm to about 1,000 ppm, preferably from about 10 ppm to about 1,000 ppm and more preferably from about 100 ppm to about 500 ppm.
- the amount of aromatic triazole corrosion inhibitor in the aqueous treating fluid is monitored fluorometrically and additional inhibitor is added to the fluid to ensure that the aromatic triazole concentration in the fluid remains within the effective range as described above.
- the fluorimetric method is described briefly as follows.
- the fluorescence intensity of the aqueous fluid using an excitation light source at the desired emission wavelength is measured with a detector capable of measuring fluorescent light.
- Suitable excitation light sources include light sources capable of producing some light at the desired wavelength for aromatic triazoles.
- excitation light sources include xenon flashlamps, continuous xenon lamps, tungsten- halogen lamps, deuterium lamps, deuterium-tungsten lamps, mercury vapor lamps, phosphor-coated mercury vapor lamps, mercury-argon lamps, and the like.
- Acceptable detectors include, among others, photodiodes, phototransistors, photocells, photovoltaic cells, photomultiplier tubes, charge-coupled devices, and the like. The detector is selected based on its ability to detect light at the desired wavelength. Excitation and light sources and detectors are well known in the art and are commercially available from a variety of sources.
- the measured fluorescence intensity is then compared to a working curve drawn up using standards in the concentration range of interest and this comparison provides a precise determination of the concentration of the corrosion inhibitor in the water sample drawn from the system.
- Proper choice of excitation and emission wavelengths are essential to obtaining linearity and predictable results for fluorescence response to a range of aromatic triazole dosages.
- Table 1 shows selection of the excitation and emission wavelengths required to obtain a linear response for benzotriazole. If optical filters are chosen incorrectly, reduced linearity in fluorescence response over a narrower dosage range will occur (see Examples A-C below).
- Example D is the best combination of excitation and emission wavelengths (leading to the best linearity over a broad range of concentrations) of the four examples shown in Table 1.
- Undesirable interference may be encountered when some other species has significant fluorescence emission about the emission wavelength selected for monitoring the given corrosion inhibitor.
- the fluorescence behavior of benzotriazole at various pH values is shown in Table 2.
- the pH is measured using an Orion pH meter (Model 290 A, Orion Research, Inc., Boston, MA) calibrated with VWR Scientific Products (West Chester, PA) standard buffers at pH 4 (potassium hydrogen phthalate buffer) and pH 10 (sodium bicarbonate/carbonate buffer).
- Benzotriazole solution is prepared by dissolving powdered benzotriazole in 50 mL of isopropyl alcohol and then diluting to a volume of 1 L with distilled water (final solution 95/5 vol/vol water/isopropyl alcohol). For a 1000 ppm benzotriazole solution, 1 g of benzotriazole is used to prepare 1 L of solution.
- a broad range of benzotriazole concentrations (10-1000 ppm) have a pH range (5.0-5.7) which are within the preferred pH operating range (pH 2-8) where pH has little or no effect on benzotriazole fluorescence as shown in Table 3.
- the proper choice of cuvette or flowcell pathlength in conjunction of proper choice of excitation and emission wavelength, as determined empirically using the methods described herein, is essential to obtaining acceptable results.
- the isoemission wavelength of benzotriazole is significantly different (325 nm) versus tolyltriazole (350 nm) and these results must be individually determined for each aromatic triazole so that proper choice of fluorescence analysis conditions can be made.
- For high dosages of benzotriazole (hundreds of ppm), it is necessary to use longer wavelengths (320 nm for fluorescence excitation and 370 nm for fluorescence emission) to obtain linear fluorescence response to changes in triazole dosage as indicated in Table 1.
- the fluorometric analysis described above is used to determine the concentration of aromatic triazole corrosion inhibitor present the aqueous fluid so that additional corrosion inhibitor can be added as required to maintain the effective corrosion inhibiting concentration.
- the analysis can be conducted intermittantly, in which case a sample of the aqueous fluid is removed from the system for analysis or alternatively, a spectrofluorometer can be installed on-line for conducting the triazole analysis and dosage control at the desired intervals or continuously.
- a dual monochromator spectrofluorometer can be used for a fluorimetric analysis conducted on an intermittent basis and for on-line and/or continuous fluorescence regulating.
- the fluorometric analysis is conducted on a continuous basis.
- the fluorometer comprises monitoring and control means for automatically and continuously monitoring the concentration of aromatic triazole corrosion inhibitor in the aqueous fluid and adjusting the concentration of corrosion inhibitor as required to maintain the desired effective corrosion inhibiting concentration.
- the monitoring and control means typically includes a fluorometer for determining the concentration of aromatic triazole corrosion inhibitor in the water as described above, the flourometer including a transducer which generates an electrical signal corresponding to the inhibitor concentration and a feedback controller (monitor) connected to a fluid addition pump or valve for controlling the addition of aromatic triazole corrosion inhibitor contained in a reservoir, the pump to be activated and deactivated or the valve opened and closed, depending on a comparison of the concentration of corrosion inhibitor in the fluid, represented by the voltage signal from the transducer, to a voltage standard representing par performance of treating agent.
- a fluorometer for determining the concentration of aromatic triazole corrosion inhibitor in the water as described above
- the flourometer including a transducer which generates an electrical signal corresponding to the inhibitor concentration and a feedback controller (monitor) connected to a fluid addition pump or valve for controlling the addition of aromatic triazole corrosion inhibitor contained in a reservoir, the pump to be activated and deactivated or the valve opened and closed, depending on a comparison of the concentration of corrosion
- a preferred fluorometer has xenon flashlamp light-source to provide a broad continuous range of excitation/emission wavelengths from 200-2000 nm.
- the Xenon flashlamp is preferably activated once-per-second.and the fluorometer takes a fluorescence reading. Therefore response to changes in triazole dosage can start to occur after each second.
- the optical filters (excitation and emission wavelengths) are preferably exchangeable in order to optimize the optical filters for the system being monitored/controlled.
- a preferred excitation optical filter is about 320 nm.
- the preferred emission optical filter is about 370 nm.
- optical wavelength values are acceptable (for example about 280 to about 320 nm excitation and about 360 to about 375 nm emission wavelengths) depending on the concentration range of aromatic triazole to be measured and controlled.
- Exchangeable optical filters are available, for example, from Andover Corporation, Salem, NH. Any type of detector may be suitably employed so long as it is sensitive in the emission wavelength range of the desired aromatic triazole corrosion inhibitor. A photodiode detector is preferred.
- the fluorometer may also include a thermocouple to provide temperature- compensation for the effects of temperature on the fluorescence of the fluid sample. Such compensation may be necessary if the temperature of the fluid sample changes significantly, as certain aromatic triazoles such as triazole have a fairly large temperature coefficient.
- the fluorometer preferably includes a series of alarms to determine when error conditions such as high corrosion inhibitor concentration, low corrosion inhibitor concentration, fluid addition pump on too long, low flow rate of sample, sample too hot, etc. have occurred.
- the alarms are associated with "failsafe" operation of dosage control whereby dosage is controlled on a timed basis when an alarm occurs.
- the monitoring and control means may also include an output recording device or other register that generates a continuous record of triazole aromatic triazole corrosion inhibitor concentration as a function of time.
- a preferred monitoring and control means is the TRASAR® Xe-2 Controller, available from Ondeo Nalco Company, Naperville, IL.
- FIG. 3 shows an embodiment of this invention where the treatment bath 4 is equipped with means 12 for fluorometrically monitoring and controlling the concentration of aromatic triazole corrosion inhibitors in the treatment bath where the monitoring and control means 12 are disposed along the fluid transfer line 6.
- the monitoring and control means 12 include a flowcell 15 that is installed in the fluid transfer line 6 so that fluid circulating through the fluid transfer line 6 flows through the flowcell 15.
- a preferred flowcell is a hollow fused quartz cylinder (tube) with an inner- diameter (ID) of about 3 mm and outer-diameter (OD) of about 5 mm with a wall thickness of about 1 mm.
- the fused quartz flowcell is about 8.5 cm long and has o- rings around each end to seal the flowcell to the flowcell housing to ensure no leakage of fluid from the sample being analyzed.
- Light from the fluorescence excitation light, source shines through the flowcell and excites the aromatic triazole corrosion inhibitor in the aqueous fluid.
- the fluorescent emission light then shines through the flowcell and out to a detector.
- the control means generates a control signal, designated as a dashed line in FIGS. 3 and 4, that activates a valve 3 or fluid addition pump (not shown) disposed between the aromatic triazole corrosion inhibitor supply reservoir 1 and treatment bath 4.
- the control means automatically activates and deactivates the pump or opens and closes the valve to add corrosion inhibitor to maintain its concentration in the fluid in the desired concentration range.
- this invention is a treatment bath for copper plated or metallized semiconductor devices comprising an inlet, an outlet, a fluid transfer line connecting said inlet and outlet for circulating aqueous fluid containing one or more aromatic triazole corrosion inhibitors through said treatment bath and fluid transfer line and monitoring and control means for fluorometrically determining the concentration of aromatic triazole corrosion inhibitor in the aqueous fluid, wherein the monitoring and control means comprise a flowcell installed in the fluid transfer line.
- the treatment bath further comprising a supply reservoir containing an aqueous solution of aromatic triazole corrosion inhibitor and a valve or pump for controlling the addition of the aqueous solution of aromatic triazole corrosion inhibitor to the treatment bath.
- monitoring and control means 12 are disposed along a side-stream sample line 13 connected to a treatment bath fluid transfer line 6 through a side-stream sample line 13 and pump 14.
- Pump 14 can be activated as necessary to provide a continuous or intermittant flow of fluid through a flowcell 15 installed in the side-stream sample line 13.
- this invention is a treatment bath for copper plated or metallized semiconductor devices comprising an inlet, an outlet, a fluid transfer line connecting said inlet and said outlet for circulating an aqueous fluid containing one or more aromatic triazole corrosion inhibitors through said treatment bath and fluid transfer line, a side-stream sample line for removing a sample of aqueous fluid from the fluid transfer line and monitoring and control means for fluorometrically determining the concentration of aromatic triazole corrosion inhibitor in the aqueous fluid, wherein the monitoring and control means comprise a flowcell installed in the side-stream sample line.
- the aqueous treating fluid used in semiconductor device manufacturing processes comprises ultrapure water.
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Abstract
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Priority Applications (1)
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EP04754548A EP1660954A4 (en) | 2003-07-11 | 2004-06-07 | Method of inhibiting corrosion of copper plated or metallized surfaces and circuitry during semiconductor manufacturing processes |
Applications Claiming Priority (2)
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US10/617,467 US20050008532A1 (en) | 2003-07-11 | 2003-07-11 | Method of inhibiting corrosion of copper plated or metallized surfaces and circuitry during semiconductor manufacturing processes |
US10/617,467 | 2003-07-11 |
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WO2005015608A2 true WO2005015608A2 (en) | 2005-02-17 |
WO2005015608A3 WO2005015608A3 (en) | 2005-06-16 |
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PCT/US2004/017977 WO2005015608A2 (en) | 2003-07-11 | 2004-06-07 | Method of inhibiting corrosion of copper plated or metallized surfaces and circuitry during semiconductor manufacturing processes |
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US (1) | US20050008532A1 (en) |
EP (1) | EP1660954A4 (en) |
KR (1) | KR20060082789A (en) |
CN (1) | CN1820231A (en) |
TW (1) | TW200502438A (en) |
WO (1) | WO2005015608A2 (en) |
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US20070238821A1 (en) * | 2006-04-11 | 2007-10-11 | Houlihan Francis J | Anti-tarnishing device |
US20080145271A1 (en) * | 2006-12-19 | 2008-06-19 | Kidambi Srikanth S | Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces |
US20090319195A1 (en) * | 2008-06-20 | 2009-12-24 | Hoots John E | Method of monitoring and optimizing additive concentration in fuel ethanol |
US8470238B2 (en) * | 2008-11-20 | 2013-06-25 | Nalco Company | Composition and method for controlling copper discharge and erosion of copper alloys in industrial systems |
US8418757B2 (en) * | 2010-05-06 | 2013-04-16 | Northern Technologies International Corporation | Corrosion management systems for vertically oriented structures |
JP5588786B2 (en) * | 2010-08-24 | 2014-09-10 | 出光興産株式会社 | Silicon wafer processing liquid and silicon wafer processing method |
JP5716706B2 (en) * | 2012-05-28 | 2015-05-13 | 栗田工業株式会社 | Corrosion control method in sealed cooling water system |
WO2014031389A1 (en) * | 2012-08-22 | 2014-02-27 | Franklin Fueling Systems, Inc. | Method and apparatus for limiting acidic corrosion in fuel delivery systems |
WO2016006435A1 (en) * | 2014-07-10 | 2016-01-14 | ボッシュ株式会社 | Motor module and abs hydraulic unit |
EP3256693A4 (en) | 2015-02-10 | 2018-12-19 | Ecolab USA Inc. | Corrosion inhibitors and kinetic hydrate inhibitors |
JP6472726B2 (en) * | 2015-07-22 | 2019-02-20 | 東京エレクトロン株式会社 | Substrate liquid processing apparatus, substrate liquid processing method, and storage medium |
US11352248B2 (en) | 2017-03-07 | 2022-06-07 | Franklin Fueling Systems, Llc | Method and apparatus for limiting acidic corrosion and contamination in fuel delivery systems |
US11365113B2 (en) | 2017-03-07 | 2022-06-21 | Franklin Fueling Systems, Llc | Method and apparatus for limiting acidic corrosion and contamination in fuel delivery systems |
US10072871B1 (en) * | 2017-03-10 | 2018-09-11 | Haier Us Appliance Solutions, Inc. | Corrosion inhibitor module for a packaged terminal air conditioner unit |
WO2019135991A1 (en) | 2018-01-03 | 2019-07-11 | Ecolab Usa Inc. | Benzotriazole derivatives as corrosion inhibitors |
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GB1496657A (en) * | 1974-01-11 | 1977-12-30 | Sandoz Ltd | Metering system |
US4992380A (en) * | 1988-10-14 | 1991-02-12 | Nalco Chemical Company | Continuous on-stream monitoring of cooling tower water |
US5278074A (en) * | 1992-04-22 | 1994-01-11 | Nalco Chemical Company | Method of monitoring and controlling corrosion inhibitor dosage in aqueous systems |
US5435969A (en) * | 1994-03-29 | 1995-07-25 | Nalco Chemical Company | Monitoring water treatment agent in-system concentration and regulating dosage |
US5503775A (en) * | 1994-05-09 | 1996-04-02 | Nalco Chemical Company | Method of preventing yellow metal corrosion in aqueous systems with superior corrosion performance in reduced environmental impact |
US6060318A (en) * | 1997-06-11 | 2000-05-09 | Nalco Chemical Company | Tracing of process additives in industrial ceramics applications |
US5922606A (en) * | 1997-09-16 | 1999-07-13 | Nalco Chemical Company | Fluorometric method for increasing the efficiency of the rinsing and water recovery process in the manufacture of semiconductor chips |
US6117795A (en) * | 1998-02-12 | 2000-09-12 | Lsi Logic Corporation | Use of corrosion inhibiting compounds in post-etch cleaning processes of an integrated circuit |
US6255123B1 (en) * | 1998-11-17 | 2001-07-03 | Kenneth P. Reis | Methods of monitoring and maintaining concentrations of selected species in solutions during semiconductor processing |
US6274478B1 (en) * | 1999-07-13 | 2001-08-14 | Motorola, Inc. | Method for forming a copper interconnect using a multi-platen chemical mechanical polishing (CMP) process |
US6488038B1 (en) * | 2000-11-06 | 2002-12-03 | Semitool, Inc. | Method for cleaning semiconductor substrates |
US6799589B2 (en) * | 2000-11-08 | 2004-10-05 | Sony Corporation | Method and apparatus for wet-cleaning substrate |
US6436711B1 (en) * | 2000-12-13 | 2002-08-20 | Nalco Chemical Company | Fluorometric control of aromatic oxygen scavengers in a boiler system |
US6762832B2 (en) * | 2001-07-18 | 2004-07-13 | Air Liquide America, L.P. | Methods and systems for controlling the concentration of a component in a composition with absorption spectroscopy |
US6726535B2 (en) * | 2002-04-25 | 2004-04-27 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method for preventing localized Cu corrosion during CMP |
-
2003
- 2003-07-11 US US10/617,467 patent/US20050008532A1/en not_active Abandoned
-
2004
- 2004-06-07 KR KR1020057022044A patent/KR20060082789A/en not_active Application Discontinuation
- 2004-06-07 EP EP04754548A patent/EP1660954A4/en not_active Withdrawn
- 2004-06-07 CN CNA2004800195339A patent/CN1820231A/en active Pending
- 2004-06-07 WO PCT/US2004/017977 patent/WO2005015608A2/en active Search and Examination
- 2004-06-24 TW TW093118344A patent/TW200502438A/en unknown
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EP1660954A4 (en) | 2009-04-15 |
KR20060082789A (en) | 2006-07-19 |
CN1820231A (en) | 2006-08-16 |
US20050008532A1 (en) | 2005-01-13 |
TW200502438A (en) | 2005-01-16 |
EP1660954A2 (en) | 2006-05-31 |
WO2005015608A3 (en) | 2005-06-16 |
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